Protecting material{3 s with organo-bismuth compounds

ABSTRACT

This invention relates to germicidal finishes for substrates subject to the accumulation or growth of microorganisms, methods for applying such finishes and to the substrates so finished. The invention further relates to germicidal or bacteriacidal or bacteriastatic compositions such as detergent compositions and to processes for employing the same. The germicidal agents are certain organo-bismuth compounds.

[ PROTECTING MATERIAL'S WITH ORGANO-BISMUTH COMPOUNDS [75] lnventor: Frank J. Gross, Union County, NJ. [73] Assignec: American Cyanamid Company,

Stamford, Conn. 122] Filed: Sept. 7, 1965 [21] Appl. N0.: 485,581 Related US. Application Data [63] Continuation'in-part of Ser. No. 193,004, May 7,

1962, abandoned, which is a continuation-in-part of Ser. No. 120,508, June 29, 1961, abandoned.

[52] US. Cl 424/296, 8/137, 8/142, 106/15 AF, 117/138.5, 117/138.8, 117/139, 117/142, 117/143,117/154, 162/161, 252/8.6, 252/8.8, 252/106 [51] Int. Cl A0ln 9/12, A611 13/00, AOln 9/24, A01n 9/00 [58] Field of Search 260/447; 424/296;

1.111 3,862,326 1 1 Jan. 21, 1975 References Cited UNITED STATES PATENTS 2,221.339 11/1940 Allison 167/30 ux Primary Eranziner-$tanley ,1 Friedman Assistant Examiner-Dale R, 0w Arlorne). Agent. or Firm-lohn 1i. Hanrahan [57] ABSTRACT I This invention relates to germicidal finishes for substrates subject to the accumulation or growth of mi- I fi claims, N0 Drawings PROTECTING MATERIALS WITH ORGANO-BISMUTH COMPOUNDS This application is a continuation-in-part of application Ser. No. l93,004 filed May 7, 1962, which in turn was a continuation-in-part of application Ser. No. 120,508 filed June 29, 196i and both now abandoned.

The present invention relates to germicidal finishes for substrates subject to the accumulation or growth of microorganisms, methods for applying such finishes and to the substrates so finished. In a particular and preferred aspect the present invention relates to the impartation of a durable germicidal finish to cellulose substrates, such as cellulose textile material, paper, wood and the like, to the processes for applying such finishes, and to said cellulose substrates characterized by such a finish.

While the present invention will be described primarily in conjunction with the impartation of germicidal finishes for textile substrates, since this is an area of outstanding performance and utility, it should be kept in mind, as will be seen from the examples hereinafter, that substrates subject to the accumulation or growth of microorganisms are in general contemplated, e.g., plaster, metal, rubber, plastic, painted surfaces, skin (human or animal), leather, glass and the like. It thus becomes evident that articles such as floors, walls, doorknobs, childrens toys or articles, furniture, bathroom fixtures, school equipment and various other articles may be rendered germicidal.

In recent years, increased attention has been given to the development of textile finishes which have become known as purifying finishes. Such finishes are intended to reduce the number of microorganisms residing on the material whereby such material may be used with less danger from harmful bacteria. These purifying finishes, when applied to articles of clothing worn close to the body, are also helpful in reventing the development of body odors. A satisfactory purifying finish should be durable and active at low concentrations against a broad spectrum of microorganisms. It preferably should be non-toxic and. non-allergenic. It should not have a tendency to sensitize the wearer or person coming in contact therewith and it should not have the property of allowing strains of bacteria to develop which are resistant to the antibacterial agent of the finish. Such purifying finishes should impart little or no color to textile materials finished therewith and should be stable with respect to color and activity for substantial periods under storage and shipping conditions. It should be resistant to the conditions used in laundering and dry cleaning and should impart little or no modifi cation of the hand of textile materials. It should be substantive to fibers and therefore durable to laundering, not merely a coating, and compatible with dyes and resins normally found or employed in the resin finishing of textile materials. Additionally, such compounds should be stable to oxidation by air, light and heat or remain germicidally effective in an oxidized state.

Many of the purifying finishes available today such as neomycin, as the sulfate or other salt thereof, hexachlorophene, salts and complexes of mercury and others can be used in the treatment of textile materials but some are not completely satisfactory, particularly in regard to their durability to washing and laundering. In this connection, the germicidal effectiveness of some of these finishes is greatly reduced by laundering operations in which chlorine bleach is employed, Thus, some purifying finishes which are on a substrate like textile materials are inactivated by laundering operations in which chlorine is employed. Other purifying agents which are otherwise capable of being applied from solutions containing surface active agents such as detergents or softeners are inactivated if the solution also contains chlorine as a bleaching agent. Thus many germicides may not be formulated with chlorine or chlorine generating bleaching agents.

' Many of the germicides now being employed are safe within the generally accepted meaning of that term. However, it is always highly desirable to employ a material which is not only highly effective as a germicide, but in addition is characterized by low toxicity.

Further, with respect to certain of the purifying finishes now available it has been found that durable germicidal finishes result when they are applied to cellulosic textile materials or cellulosic substrates, while the application of these same purifying agents to noncellulosic substrates such as textile materials composed of the synthetic fibers, as for example the nylon, acrylic, and polyester fibers, results in finishes which have poor durability. Such finishes are therefore not successful on such substrates.

Further, many of the available purifying finishing materials are continuously removed from textile materials when the textile materials are repeatedly laundered,

even when the laundering mediums contain, in addition I to detergents, amounts of the germicide. In this regard, it should be noted that many germicidal materials may either not be compatible with surface active agents such as detergents or softeners or their effectiveness is masked or neutralized by. the presence of such materials.

OBJECTS OF. THIS INVENTION Accordingly it is an object of the present invention to provide a purifying finish for various substrates, and in particular for cellulose substrates and textile materials in which finishes possessing the desirable characteristics of a purifying finish described above are obtained. It is a particular object to provide such a finish for textile materials which is characterized by unusually good durable activity when materials treated therewith are subjected to repeated cleaning operations such as dry cleaning and home or commercial laundering.

It is a further object to provide a purifying agent which in a laundering medium is not deactivated by chlorine, and to therefore provide a purifying agent which may be readily employed in and applied from laundering solutions.

A further object is to provide a purifying agent which, because of its compatibility, can actually be formulated with bleaching agents and in particular chlorine generating bleaching agents.

Another object of this invention is to provide a purifying agent which may be characterized as being of low toxicity when compared with many known germicides.

A still further object of the present invention is to provide a purifying finish for textile materials, the activity of which, instead of being diminished by laundering operations employing detergent formulations containing such a germicide, is actually increased or builds up as a result of such repeated launderings.

It is another object of this invention to provide a finish for textile materials, the activity of which is not diminished as a result of the use of chlorine bleach in laundering operations for the same, and which finish may to some extent be said to be enhanced.

Another object of the present invention is to provide a germicidal-detergent formulation in the use of which the germicidal activity is not masked or neutralized by detergents.

An object of the present invention is to provide germicidal agents which may be employed with various nonionic, anionic or cationic materials, particularly surface active agents such as detergents and softeners, to substantial advantage, including illustratively enhanced germicidal activity and softening at low concentrations of germicidal agent, and antifungal finishes.

A still further object of the present invention is to provide a germicidal finish for textile materials which is compatible with a broad range of thermosetting resins normally employed by the textile finishing industry to impart crease resistance and dimensional stability to textile materials, thereby enabling such materials to be rendered wrinkle resistant and dimensionally stable while at the same time having a purifying finish thereon.

These and other objects and advantages of the present invention will become more apparent from the detailed description thereof set forth hereinbelow.

THE INVENTION of those having the following formulae:

Aryl Aryl X -Y'Bl YB1 where Y and Z are selected from the group consisting of halogen, aryl or aryl-A; wherein the aryl groups are aryl radicals (including substituted aryl); A is a heteroatom selected from the group consisting of S and O; and X and X are selected from the group consisting of monovalent atoms, monovalent radicals, and when X and X are taken together, divalent atoms and divalent radicals.

The organo-bismuth compounds contemplated for use in the present invention are those compounds meeting the classical definition of organometallic compounds, that is, those having at least one carbon metal bond. Thus, such compounds contemplated for use in the present invention exclude salts of organic acids, i.e., most ionic bondings including metal alkoxides and the like, and compounds where the bonding to carbon is only through heteroatoms such as O or S. Coordination or chelate compounds are also excluded.

TYPICAL ORGANO-BISMUTH COMPOUNDS Typically the organo-bismuth compounds contemplated for use in the present invention may be classed according to any of the eight general formulae set forth hereinbelow along with a number of typical illustrative examples of the unknowns M and N in said formulae.

(l) Aryl Aryl-Bi Aryl Aryl

Aryl-M-Bt Aryll1i Aryl In the illustrative formulae above the aryls may be the same or different and typically equal phenyl, tolyl, naphthyl, including substituted aryls where the substituting group is typically halogen (Cl, Br, F, 1), alkoxy, alkyl, hydroxy and the like, M is a heteroatom such as O or S, and the Ns are typically halogen, OH, and the like.

Illustratively the organo-bismuth compounds con templated for use in the present invention include: Formula 1 triphenylbismuthine, tri-ptolylbismuthine, tris-(p-chlorophenyl)bismuthine, tris- (p-bromophenyl)-bismuthine, tris-(p-fluorophenyl)bismuthine, tris-(p-methoxyphenyl)bismuthine, bis-(pchlorophenyl)-p-tolylbismuthine, p-hydroxyphenyldiphenylbismuthine, 1-naph-thyldiphenylbismuthine, tri-l-naphthylbismuthine, tris(alpha, alpha, alphatrifluoro-m-tolylbismuthine; Formula 2 phenylbis(phenylthio)bismuthine, bis(phenylthio)-ptolylbismuthine, (p-chlorophenyl)bis(phenylthio)bismuthine;

Formula 3 diphenyl(phenylthio)bismuthine; Formula 4 triphenylbismuth dichloride, diphenyl-ptolylbismuth dichloride, triphenylbismuth dibromide, triphenylbismuth difluoride, triphenylbismuth dinitrate, triphenylbismuth hydroxy chloride, triphenylbismuth carbonate, triphenylbismuth sulfate, triphenylbismuth diacetate, triphenylbismuth dibenzoate, triphenylbismuth oxide, tris(alpha, alpha, alphatrifluorom-tolylbismuth dichloride, triphenylbismuth dipropionate, triphenylbismuth diformate, triphenylbismuth didecanoate, triphenylbismuth didodecanoate, triphenylbismuth distearate, triphenylbismuth dimethacrylate, triphenylbismuth bis(chloroacetate), triphenylbismuth bis(trifluoroacetate), triphenylbismuth bis[p- 3-(3,4-dichlorophenyl)ureidobenzoatel], triphenylbismuth phthalate, triphenylbismuth dianthranilate, triphenylbismuth bis(5chloroanthranilate), triphenylbismuth bis(p-chlorobenzoate), triphenylbismuth disalicylate, triphenylbismuth bis(3,5-dichlorosalicylate), triphenylbismuth di-p-toluate, triphenylbismuth bis(mnitrobenzoate), triphenylbismuth bis(p-toluenesulfonate);

Formula 5 chlorodiphenylbismuthine, iodobis(pchlorophenyl)-bismuthine; Formula 6 dichlorophenylbismuthine;

Formula 7 diphenylbismuth trichloride; Formula 8 bis(p-nitrophenoxy)triphenylbismuth, bis(pbromophenoxy)-triphenylbismuth, bis(phenylthio)triphenylbismuth, bis(2,4,6-tribromophenoxy)triphenylbismuth, bis(pentachlorophenoxy)triphenylbismuth, bis(o-nitrophenoxy)triphenylbismuth and the like.

The preferred organo-bismuth compounds employable in accordance with this invention are triphenylbismuthine, triphenylbismuth dichloride and triphenylbismuth hydroxy chloride.

The above illustrative organo-bismuth compounds or their equivalents may be employed singly or in combination with one another in accordance with the present invention.

METHODS OF APPLICATION The organo-bismuth compounds of this invention may be applied to the various substrates from organic solvents or from aqueous emulsions or dispersions, formulations which may or may not contain surface active materials such as detergents, softeners and the like, by conventional application procedures, such as spraying, wiping, painting, brushing, dipping and the like. Thus, in the textile finishing industry these organo-bismuth compounds may be applied by padding, spraying, immersion, dipping and the like. In addition, while in accordance with the present application it is preferred to paper substrates, they may be incorporated into paper by the addition to the pulp from which the paper is formed or to the formed paper as by spraying thereon. In addition, they maybe applied to formed paper during calendering or sizing operations.

APPLICATION TO TEXTILE MATERIALS In addition to the application of the organo-bismuth compounds of this invention to various substrates such as textile materials during detergent or laundering operations, the compounds contemplated for use in the instant invention are uniquely compatible and stable with a large number of the conventional resins and reactants employed in the creaseproofing and stabilization of cellulosic textile materials. In this regard, it has been surprisingly found that the organo-bismuth compounds are compatible or may be rendered compatible with treating bath formulations containing typical thermosetting creaseproofing resins and may accordingly be applied simultaneously with said resins to impart both a creaseproofing and purifying finish to the textile material. In addition, the organo-bismuth compounds of this invention may be applied both prior or subsequent to the application of creaseproofing resins to cellulose containing textile materials.

By textile materials," as that term is employed herein, it is meant fibers, filaments or fabrics whether they be knitted, woven, felted or otherwise formed and prepared from such fibrous material as cotton, rayon, linen, jute, hemp, ramie, silk, acetate, polyamide fibers,

The organo-bismuth compounds contemplated for use in the present invention are employed in amounts which are effective for the intended purpose, namely as a purifying finish on the substrates contemplated. Normally, the bismuth compounds may be applied in amounts of from 0.0001 to about 2.5% based on the weight of the substrate, as for example on the weight of the textile material or fabric while in the dry state. Preferably the amount applied is from between about 0.1 to about 0.5% based on the weight of the substrate. The substrate may be dried at ambient temperatures or at temperatures up to temperatures that will result in the degradation of the substrate. Normally in the case of textile materials temperatures of the order of from ambient temperatures totemperatures up to 400 to 450F. may be employed which are about optimum for textile materials which are able to stand such temperatures since little, if any, advantage is gained by employing higher temperatures and most conventional textile finishing equipment is best used at temperatures less than 450F. The time for drying is for the most part inversely proportional to the temperature at which drying is effected and of course depends on thenature of the substrate and the materials of which it is made. Most preferably, however, employing drying temperatures of from between to 350F. and times of between about 1.5 and 6 minutes will be required for textile materials of typical weight. Preferably temperatures of between about 225 and 250F. will be employed with times between about 1.5 and 2 minutes. Whether the organo-bismuth compound is applied alone or whether it is applied from any of the compositions illustratively proposed above, drying of textile material may be carried out substantially the same.

APPLICATION WITH SURFACE ACTIVE AGENTS (DETERGENTS, SOFTENERS ETC.)

In accordance with a specific aspect, the bismuth compounds of this invention may be applied with advantage with surface active agents and particularly detergents and/or softeners in normal washing, laundering or dry cleaning procedures in that at least to some extent they appear to be substantive to textile materials and to result in build up" on the materials so processed. Obviously, detergent formulations containing these compounds may be employed to clean numerous substrates other than textile material and thus provide a means for imparting a germicidal finish thereto. With respect to the aspect of this invention relating to the application of organo-bismuth compounds from baths containing detergents and softeners, it should be noted that such compounds may be incorporated into detergent formulations, softener formulations or formula tions containing detergents and softeners, or simply added to the laundering medium containing the same,

including such laundering mediums containing chlorine.

The organo-bismuth compounds contemplated for use in the present invention are compatible with or may be employed with various non-ionic, anionic and cationic materials or surface active agents. Anionic, cationic and non-ionic surface active agents have many uses, including wetting, penetrating, emulsifying, dispersing, solubilizing, foaming, frothing, washing or scouring, textile softening, and the like.

As is generally known, a surface active agent may be represented as having two parts; one part being made up of a long hydrocarbon chain that is oil-soluble and virtually insoluble in water (hydrophobic), the other is a strongly water-soluble group (hydrophilic). In anionic surface active agents, the hydrophobic portion carries a negative charge when in aqueous solution and in the cationic surface active agents the hydrophobic portion has a positive charge. In the non-ionics the water solubilizing group is non-ionic, as for example in ethers, esters and the like.

APPLICATION WITH DETERGENTS Anionic and non-ionic surface active agents have extensive uses as detergents, especially detergents for textile use, but also for cleaning hard surfaces.

The anionic detergents which may be used in the composition of this invention include alkali metal salts of fatty acids, e.g., soaps, alkali metal sulfonates and sulfates. A preferred group of anionic detergents are the long chain alkyl aryl sulfonates, that is, those wherein the alkyl group is straight or branched in structure and contains from 8 to 22 carbon atoms but preferably 10 to 16 carbon atoms. Examples of such alkyl groups include octyl, decyl, dodecyl, hexadecyl, octadecyl, mixed long chain alkyl groups derived from long chain fatty acids such as the lauryl radical, polymers of low monoolefins such as propylene tetramer, propylene hexamer and the like. The aryl group in such alkyl aryl sulfonates may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene and the like. Specific examples of such compounds include sodium dodecylbenzenesulfate, sodium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, and the sodium hexadecylbenzenesulfonate.

The well-known sulfate detergents having 8 to 26 carbon atoms and particularly those having an alkyl radical of about 12 to 22 carbon atoms may be employed as anionic detergents in the compositions of my invention. Such sulfates include sodium coconut oil monoglyceride monosulfate, sodium tallow diglyceride monosulfate, sodium lauryl sulfate and sodium alkyl sulfate.

The above and numerous other surface active sulfonates and sulfates known to those skilled in the art may be employed singly or in combination with one another and with their equivalents in accordance with the present invention.

Typical of the non-ionic surface active agents which may be employed in combination with the organobismuth compounds of this invention are those which may be described as viscous liquids, wax-like water soluble surface active substances containing a polyglycol ether group of the structure in which Z, and Z are hydrogen or a short chain alkyl, p is an integer greater than three and Z is a residue of a monomeric organic compound having an active hydrogen, as for example, an alcohol, a phenol, an amide, a primary amine, a secondary amine, a carboxylic acid or the like. These non-ionic detergents are well known (e.g., US. Pat. Nos. 1,970,578 and 2,213,477) and may be typified by polyalkylene oxide derivatives (e.g., polyethylene oxide, polypropylene oxide, polybutylene oxide) of water insoluble higher fatty acids, such as lauric, oleic, palmitic and stearic and the likeor mixtures thereof such as the mixtures of fatty acids obtained from animal and vegetable fats and oils and by the oxidation of petroleum fractions such as paraffin wax. They may also be exemplified by the polyalkylene oxide derivatives of such water insoluble organic hydroxy compounds as higher aliphatic alcohols (i.e., the alcohols corresponding to the fatty acids specified above or mixtures thereof), phenols, particularly alkyl phenols containing at least six alkyl carbon atoms such as isooctyl, triisopropyl, nonyl, dodecyl, octadecyl phenols or naphthols, or of aralkyl alcohols such as benzyl alcohol, cinnamyl alcohol and the like. They may also be exemplified by the polyalkylene oxide derivatives of such amines as stearyl, lauryl, dicyclohexyl, dibutyl amine and the like. A particularly useful non-ionic detergent is that obtained by condensing one mole of tall oil with 515 moles of ethylene oxide.

Detergent-germicidal compositions of this invention should contain from about 0.001% up to about 5% of the germicidal compounds of this invention, based on the weight of the detergent in the composition and preferably from 0.01% to 1% based on said weight. It should be noted that the t.-rm composition illustratively is expressly intended to include bars of soap or detergent containing such germicidal compounds as well as soap powders and powdered detergent formulations or liquid soap or liquid detergent formulations. Normally, compositions will contain in addition to the surface active agent or detergent and thev germicidal compound various fillers or diluents and buffers or builders, as for example tetrasodium pyrophosphate, sodium sulfate, sodium perborate and the like. Thus, typical formulations contemplated by this invention might normally have the following components:

In a laundering operation employing the detergentgermicidal compositions of this invention, the aqueous laundering medium should contain an amount of about 0.000l to about 1.0% by weight ofthe germicide based on the dry weight of the fabric being laundered. Germicidal compounds of this invention present in these amounts in laundering mediums exhaust readily and become attached to the fibers in amounts from between about 0.0001 and 1.0% and give excellent contact protection against Staphylococcus aureus. While the general range of from between 0.0001 and l.0% of the germicidal compound of this invention based on the dry weight of the cellulosic textile materials produces outstanding germicidal effects, concentrations of from .001 to 0.1% are generally preferred.

APPLICATION WITH SOFTENERS Softness is a physical characteristic of textiles that is highly esteemed. Large amounts of surface active agents, including anionic, cationic and non-ionic sur face active agents, are used as textile softeners. This is in contrast with surface active agent detergents in that cationic surface active agents are rarely employed as detergents, particularly in conjunction with textiles, in that they tend to redeposit soil on the textile materials. The hydrophobic portion of textile softeners is generally dodecyl, tetradecyl, hexadecyl, octadecyl or heptadecenyl. The available (commercial) hydrophilic groups are, for the anionic softeners, sulfate (50,), sulfonate (S0 phosphate (P0,), and carboxyl (COOH); for the cationic softeners, substituted amine and ammonium (NH R, NI-I R Nl-lR and NR,,); and for nonionic softeners polyoxyethylene (Cg-I 0) and polyoxypropylene (C l-I 0). Other solubilizing groups may of course be present.

Anionic softening agents are only slightly absorbed by most textiles from aqueous solutions. This is because most textiles are anionic and tend to repel the anionic softeners.

In contrast, cationic softeners are attracted by most textile fibers and are substantive to such fibers. Low concentrations in the bath thus can normally produce the requisite finishing effect. These are therefore the most important softening agents used in textile finish- The non-ionic softeners are becoming increasingly important because of their compatibility with other finishing and dyeing agents and assistants.

Of particular interest among the anionic softeners are the sulfonated tallows and other soaps, also sulfated oils and tallows and sulfated fatty alcohols. Of the nonionics, the fatty acid ethylene oxide condensates are particularly important.

The cationic softeners are characterized by their substantive properties and by their efficiency of softening action. In addition to their use as softening agents, cationic surface active agents have other uses as textile finishes. These include use as antistatic and bacteriostatic or mildew resistant finishes. The antistatic finishes have most value on hydrophobic synthetic fibers.

Several classes of cationic surface active agents have been used commercially in textile finishing. Some of these are: I

l. Salts of Simple Primary Amines:

Octadecylamine acetate Hexadecylamine acetate 2. Salts of Simple Tertiary Amines:

N,N-Dimethylhexadecylamine acetate 3. Quaternary Ammonium Salts:

Hexadecyl dimethyl benzyl ammonium chloride Octadecyl dimethyl benzyl ammonium chloride Octadecyl trimethyl ammonium chloride Didodecyl dimethyl ammonium chloride Dioctadecyl dimethyl ammonium chloride Dihydrogenated tallow dimethyl ammonium chloride Di-coco dimethyl ammonium chloride 4. Salts of Amino Amides:

N-Stearoyldiethylenetriamine diacetate 5. Quaternary Ammonium Salts of Amino Amides: N-(Z-Diethylaminoethyl)stearamide ethosulfate 6. Salts of lmidazolines:

2-Heptadecyl-3-(Z-aminoethyl)imidazoline diacetate 7. Quaternary Derivatives of lmidazolines:

2-Heptadecyl-3-imidazolinyl 2-hydroxyethyl carboxymethyl ammonium chloride 8. Salts of Amino Esters:

N-Bis(2-hydroxyethyl)-2-aminoethyl stearate 9. Quaternary Salts of Amino Esters The organo-bismuth compounds contemplated by this invention may be employed with any of the above cationic surface active agents. Of particular interest as softeners, especially for home laundering operations, are the quaternary ammonium compounds, especially those of classes 3 and 7 set forth above.

Whether the organo-bismuth compound is employed with a detergent-surface active agent or a softenersurface active agent, the lower limit for activity on the weight of the substrate and in particular the fabric is as a practical matter about 0.001%.

It is an interesting facet of this aspect of the present invention that employing softeners in combination with the organo-bismuth compounds in applications by exhaustion, effective germicidal-soft finishes are obtained even with very low bath concentrations of the organobismuth compound. Padding may be effectively used at higher bath concentrations.

APPLICATION WITH TEXTILE RESINS As noted hereinabove, the organo-bismuth compounds are employable with a wide variety of thermosetting resins of the type normally employed in the creaseproofmg of cellulose containing textile materials. As will be evident from the examples hereinafter, the organo-bismuth compounds may be applied simultaneously with the creaseproofmg resins, prior to, or subsequent to, the application of such resins to the textile substrates.

Typically the desired thermosetting resin is an aminoplast. As examples of suitable thermosetting aminoplast resins contemplated for use in accordance with this aspect of the present invention, the water soluble mela mine formaldehyde resins prepared in accordance with US Pat. No. 2,197,357 and 2,529,856 are contemplated. Examples of such resins are tris(methoxymethyl)melamine, tris(methoxymethyl)dimethylol melamine, hexakis(methoxymethyl)melamine, and the like. In addition to these malamineformaldehyde resins, the urea and thiourea-formaldehyde condensates are contemplated, as are their alkylated derivatives. Thus, for example, dimethylol urea, methylated dimethylol urea and thiourea, dimethylol ethylene urea, dimethylol 1,2- propylene urea and thiourea, dimethylol l,3-propylene urea and thiourea and other related homologous com pounds are contemplated. Additionally, the formaldehyde condensates of dicyandiamide, biuret and the like are contemplated, as are the water soluble formaldehyde condensates of thiobisamides of the type described in US. Pat. No. 2,887,408.

Guanamine-formaldehyde condensates, as for example, those described in U.S. Pat. No. 2,887,409, including the formaldehyde condensates of methoxy acetoguanamine, ethoxy acetoguanamine, tertiary butoxy acetoguanamine, and the like are contemplated.

Urons may also be employed with the compounds of this invention as, for example, N,N'bis(methoxymethyl)uron and various other and closely related compounds such as are described in US. Pat. No. 2,373,135. Additionally, -tetrahydro-s-triazones such as tetrahydro-S-(B-hydroxyethyl)-s-triazone and compounds of the type described in US. Pat. No. 2,304,624 are also fully contemplated.

The above and other equivalent creaseproofing resins may be applied to the textile material by any of the well known techniques as, for example, spraying, dipping, immersing, padding and the like in such amounts as to apply from between 1 and 25% and in some instances higher amounts may be applied based on the dry weight of the material. Preferably the amount of resin applied is from between about 3 and based on the weight of the textile material.

Normally, the-thermosetting resin is applied with a curing catalyst or accelerator. The catalyst utilized may be a free acid, acid salts, alkanolamine salts, metal salts and the like. The concentration of catalyst employed may range from about 0.1 to about 25% or higher based on the weight of the resin solids, depending upon the particular catalyst type employed. Thus, for example, from between about 0.1 and about 10% of a free acid such as phosphoric, tartaric, oxalic and the like may be employed while in the case of ammonium chloride amounts of from between 0.5 and about 10% are used. In the case of amine salts including alkanolamine salts such as diethanolamine hydrochloride from about 1.0 to about 10% are most useful while with respect to salts such as magnesium chloride, zinc chloride, zinc nitrate, aluminum chloride, amounts of from between 5 and 25% may be employed. In all instances the concentration ofthe catalyst is based on the weight of resin solids employed.

Following the application of the thermosetting resin and curing catalyst to the textile material it is subject to drying and curing operations in order to effect the properties of shrinkage control and wrinkle resistance. The drying and curing operation may be carried out in a single step or in separate steps. The temperature at which the drying and curing operations are effective varies widely and is influenced to some extent by the type of catalyst employed. Normally the range of temperatures extends from about 180 to about 450F. Generally speaking, the time of drying and/or curing operation is inversely proportional to the temperature employed and of course is influenced by whether or not separate or combined drying and curing steps are employed.

Generally when drying and curing is carried out in a combined operation a time of from about one minute to about ten minutes may be employed at temperatures from about 450 to 250F, respectively. When the material has been dried preliminary to curing, curing times of from the order of five minutes to about one-fourth minute at a temperature of from between 250 and 450F., respectively, have been successfully employed.

When the bismuth compounds are applied prior to the thermosetting resin treatment it is preferred that the treated material be first dried prior to the application, drying and curing of the resin treated goods. When the thermosetting creaseproofing resin is first ap' plied, prior to the application of the bismuth compounds, the treated fabric should be dried and cured also.

APPLICATION PROCEDURES AND TEST PROCEDURES In the examples the organo-bismuth compounds are applied alone as by a padding procedure, are applied in a washing procedure employing a detergent, are applied with thermosetting resins and thermosetting resins are applied alone, and the fabric so treated dried and cured. The procedures employed in each of these applications are outlined hereinafter and are the procedures referred to in the examples unless otherwise specifically indicated.

In addition, various washes will be referred to such as Laundromat washes (LW), Laundromat washes with chlorine (LWC), bacterial inhibiting test procedures. These procedures are set forth hereinbelow.

Drying and Curing Procedures In instances where the organo-bismuth compounds were used alone on cotton, the fabric was dried only for 2 minutes at 225F. When topped with a thermosetting resin, the fabric was dried for 2 minutes at 225F. followed by curing at 350F. for 1.5 minutes.

The synthetic fabrics treated with the bismuth compound alone were dried only for 2 minutes at 225F. When topped with thermosetting resins, they were dried for 2 minutes at 225F., then cured for 2 minutes at 290F.

For convenience, the thermosetting aminoplast resins used for topping in examples of this invention are coded as follows:

A. Methylated melamine formaldehyde resin B. Ethylene urea-formaldehyde resin C. Modified substantially fully etherified fully methylolated melamine Padding Procedure Padding applications were made by passing swatches impregnated swatches through a microset padder, obtaining approximately wet pickup on cotton and determined amounts on the various synthetic or other materials.

Washing Procedure Employing Detergent and Organo-Bismuth Compound Sufficient dimethylformamide is added to the bismuth compound to dissolve it completely. To this is added one drop of a dispersing agent (octylphenyl ethylene oxide condensate) and distilled water to the total required. (This makes a milky dispersion). Determined amounts of the bismuth dispersion (depending on the concentration required) are then added to a solution containing the detergent wherein the final combined solution contains 0.25% detergent and the required amount of bismuth compound.

Five-gram swatches of 80 X 80 untreated cotton percale are wet-out in distilled water, hand squeezed and entered into one-pint Mason jars containing 100 parts of the 0.25% detergent plus the organo-bismuth compound. The jars are capped and entered into a Launder-Ometer containing water at 135F. and the machine is run for 20 minutes, after which the swatches are removed from the jars, rinsed for minutes at 85"Fv and hand squeezed. This is repeated three times. The swatches are then air dried on a frame using circulating air from an electric fan.

Laundromat Washes (LW) Into a Laundromat washer, containing 34 liters of water at 140F., is placed a six-pound loaf of chlorinefree cotton fabrics, including the samples being tested. Three grams of neutral soap is added and the washer is run through its normal cycle of washing and rinsing (rinsing is done at 100F.).

Laundromat Washes with Chlorine (LWC) Same procedure is used as in LW except 126 ml. of a sodium hypochlorite solution (0.02% available chlorine) is added to the washing liquor.

After either type wash, the samples were removed, tumble dried and pressed on a Hoffman steam presser.

Bacterial Inhibition Test (Agar Diffusion Method) This test consists of a measurement of the purifying agents activity against a gram-positive type of bacteria (Staph. aureus) or a gram-negative type of bacteria (E. coli). Discs (11.5 mm.) of the treated fabrics are placed on an agar plate inoculated with the bacteria culture. After several hours contact, the discs are removed, and the plate incubated overnight. The activity of the purifying agent is recorded as the diameter of the clear area (in mm.) at the site of the disc an effective agent will show a clear area with a diameter greater than the disc itself (11.5 mm.) irregular extensions of the clear area are shown as values followed by p. The larger the clear area, the greater is the activity. The ac tivity under the fabric disc is also noted when there is no zone outside the area covered by the fabric. The area under the disc of the fabric is rated as follows:

C Completely clear area underneath the cloth disc.

P At least 75% clear area under the disc.

S Less than 75% clear area under the disc,

VS Less than 50% clear area under the disc.

N No clear area.

Bacterial Inhibition Test (Colony Count Test) One inch discs of treated and untreated fabrics were inoculated with a 24 hour broth culture containing the test organism (Staphylococcus aureus 209) by pipetting onto the fabric discs, a suspension of 0.1 milliliters of a suspension containing approximately 6,400 colonies of the test organism.

Immediately after inoculation the test discs were placed in a sterile drying chamber containing warm (35C.) circulating, sterile air. The discs were dried for 6 minutes, then removed from the chamber and planted on the surface of a solidified nutrient agar culture medium in previously prepared Petri dishes. An overlay of the agar nutrient was then applied to the discs by pipetting 0.3 milliliters of cooled (4245C.) molten nutrient agar. (This overlay must be applied carefully and gently so that the colonies will not be flushed off the fabric disc into the surrounding mediurns.)

The fabric discs planted in the Petri dishes were incubated at 3537C. for 48 hours in the inverted position.

. After the inoculation period the colonies that developed were counted by placing a wire grid guide over the discs in the Petri dish and thecolonies were then counted on each disc with the aid of a low power mi- EXAMPLES CONCERNED WITH TRIPHENYLBISMUTHINE OR TRIPI-IENYLBISMUTH DICHLORIDE USED ALONE OR IN COMBINATION WITH TEXTILE RESINS EXAMPLE 1 Swatches of X 80 cotton percale were treated with 1% solids (o.w.f.) of triphenylbismuthine from dimethylformamide solutions by conventional padding proce dures. The treated fabric was then dried. Portions of these fabrics were finished with 5% solids (o.w.f.) of Resin A using 12% magnesium chloride as the curing catalyst (based on the resin solids) followed by drying and curing. The treated swatches were tested for their antibacterial activity initially and after numerous washings in neutral soap (LW) or soap plus chlorine (LWC). Results are shown in Table I.

TABLE I Zones of Inhibition Solids No. of (Dia. mm.) (o.w.f.) Washes Staph. aureus 1.0 none 24.9 1.0 none 13.3 163p 1.0 5 (LW) 17.2 1.0" 5 (LW) 12.6 16.2p 1.0 5 (LWC) 19.5 1.0" 5 (LWC) P; 12.8p 1.0 15 (LW) P 1.0 15 (LWC) C; 15.5p

Good Zones of inhibition to Staph. aureus are seen after 15 washes in soap plus chlorine on the swatches treated with triphenylbismuthine only. The subsequent finishing with a thermosetting resin did not improve the durability of germicidal activity but a crease-resistant germicidally active finish was provided.

EXAMPLE 2 Concentrations of 1.0, 0.5, 0.1 or 0.01% solids triphenylbismuthine were applied to 80 X 80 cotton percale from dimethylformamide solutions by padding and drying as aforementioned. A portion of each treated fabric was topped with 5% solids thermosetting resin A, B or C plus 12% magnesium chloride (based on resin solids) as curing catalyst, followed by drying and curing. Antibacterial test results were obtained after five washes in neutral soap (LW or five washes in soap plus chorine (LWC). Results in Table ll show good durability of the zones of inhibition to Staph. aureus on the fabrics treated with triphenylbismuthine alone. Experimental results demonstrated that subsequent finishing with the thermosetting resins (A, B and C identified supra) does not as a general rule improve the durability.

TABLE 11 Zones of Inhibition Cotton 80 X 80 percale was treated with 5% solids (0.w.f.) of Resin A plus 12% magnesium chloride (based on resin solids) by padding. After drying and curing as described above, the fabrics were aftertreated with 1% solids (0.w.f.) of triphenylbismuthine from a dimethylformamide solution and then dried for 2 minutes at 225F.

Antibacterial tests were performed initially and after 5 LW or 5 LWC. Results are shown in Table 111.

TABLE 111 Zones of lnhibition 7r Solids No. of (Dia. mm.) TPB (owf) Washes Staph. aureus 1.0 none 14.8; 17.2p

1.0 5 LWc 15.7

The durability of germicidal activity is enhanced when this method of application is employed. Corresponding values at the 1% level, when the germicidal finish is topped with Resin A were 17.8 with no washing, P-C; 12.9p after 5 LW and P-C after 5 LWC.

EXAMPLE 4 Various synthetic fabrics were treated with 1% solids (o.w.f.) triphenylbismuthine. The applications were made by padding. With the exception of the fabrics of acrylic fiber and acetate fiber, which were taffeta fabrics, all applications were made to the fabrics from dimethylformamide solutions. Xylene was used on the latter two fabrics. After drying, portions of each treatment were topped with 5% solids (o.w.f.) Resin A plus 12% magnesium chloride based on the resin solids followed by drying and curing.

Results in Table IV show that good initial zones ofinhibition to Staph. aureus were obtained by the triphenylbismuthine alone with good durability to 5 washes in soap (LW) and soap plus chlorine (LWC). In general, the use of chlorine improved the zones over those obtained by using soap only. This is indeed a sur prising result. In general, topping with the thermosetting resin improved the activity initially, which is indeed unexpected, but did not add significantly to the durability of the finish.

TABLE IV Triphcnylhismuthine on Various Fabrics Zones of Inhibition "/0 Solids No. of (Dia. mm.) (o.w.f.) Washes Staph. aurcus SPUN NYLON 1.0 none 1Z.0;' 16.0p 1.0 none 17.2; 20.0p 1.0 5 LW 15.6 1.0 5 LW P-C; 13.8p 1.0 5 LWC 16.3 1.0" SLWC P; 13.4p

SPUN POLYESTER FIBER 1.0 none 15.7 1.0 none 23.0; 252p 1.0 i 5 LW P 1.0 5 LW P-C; 13.1p 1.0 5 LWC 17.0; 18.2p 1.0"" 5 LWC P; 12.5p

ACRYLlC FlBER 1.0 none 174 1.0 none 22.5; 245p 1.0 5 LW 12.8; 14.9p 1.0 S LW P-C; 12.8p 1.0 5 LWC 14.7; 162p 1.0 5 LWC P-C; 14.9p

NYLON TAFFETA 1.0 none 13.8: 15.5p 1.0" none 17.7; 19.9p 1.0 5 LW 14.6; 15.3p 1.0 S LW P-C; 14.0p 1.0 5 LWC 15.0 1.0" 5 LWC 13.2; 14.7p

ACETATE TAFFETA 1.0 none 12.9; 15.3p 1.0"" none 17.4; 200p 1.0 SLW 13.6; 15.5p 1.0 5 LW P-C; 13.7p 1.0 SLWC 13.6; 16.1p 1.0"" 5 LWC P; 14.1p

Subsequent finishing with 5% solids (n.w.f.) of Resin As has been pointed out, not only is it important that a purifying finish for textile materials be resistant to deactivation by conventional laundering aids such as chlorine bleach, but also that the purifying agents be 'not inactivated in solutions, as for example laundering EXAMPLE 5 A 20% solids oil/water emulsion was prepared as follows:

Materials Used Parts Used Triphenylbismuthine 20.0 Toluene 40.0 Oleic Acid 4.0 Morpholine 1.0 Water 35.() Total 100.0

Part A 20 parts triphenylbismuthine is dissolved in 40 parts toluene at room temperature and to this is added 4.0 parts oleic acid.

Part B 1 part morpholine is mixed with 35 parts water at room temperature using an Eppenbach highspeed stirrer. Part A is added slowly to Part B with stirring to form a stable 20% /w emulsion.

The above product was diluted and applied by pad ding to cotton, spun nylon, spun polyester, acrylic fiber, nylon taffeta, and acetate taffeta fabrics from aqueous solutions; so that 1.0% solids triphenylbismuthine was deposited on the fabrics. After drying, portions of each treated fabric were subsequently finished with 5% solids of thermosetting resin A plus 12% magnesium chloride as catalyst, followed by drying and cur- Good zones of inhibition to Staph. aureus were obtained on cotton treated with triphenylbismuthine only, with good durability to chlorine containing washes (LWC). Satisfactory zones were obtained on the synthetic fabrics with good durability to chlorine containing washes. Subsequent finishing with thermosetting resin A resin A did not significantly improve the durabilities. I

EXAMPLE 6 Triphenylbismuth dichloride was applied at 1% solids (o.w.f.) to 80 X 80 cotton and spun polyester fabric by padding from dimethylformamide solution. Portions of the cotton and spun polyester fabric were subsequently topped or finished with 5% solids (o.w.f.) thermosetting resin A plus 12% magnesium chloride as catalyst.

After drying and curing, the resin treated fabrics were washed and tested for antibacterial activity.

Good (fully comparable to triphenylbismuthine) initial zones of inhibition were obtained on the cotton fabric with good durability to 5 chlorine containing washes (LWC). Good initial zones were obtained on the spun polyester fabric with generally poorer durability to chlorine containing washes.

Subsequent finishing of the cotton or spun polyester fabric with thermosetting resin A did not significantly improve the durability.

EXAMPLE 7 A mixture of the product of Example 5 and Thermosetting Resin A was prepared as follows: Part A 7.35 parts Resin A 7.10 parts 40% magnesium chloride 35.55 parts 11 0 50.00 parts Total Part B 6.0 parts Product Example 5 0.12 part of a nonionic dispersing agent (condensation product of nonyl phenol and about 9 moles of ethylene oxide) (43.88 parts H O 50.00 parts Total) Part A was added (with stirring) to Part B. A stable product was obtained.

The above product was applied to 80 X 80 cotton by padding at 85% wet pick-up. This treatment imparted to the fabric 1% solids triphenylbismuthine plus 5% solids Thermosetting Resin A. The cotton fabric was then dried and cured. Antibacterial tests were then obtained initially. The results are in Table V below.

TABLE V initial Zone of Inhibition (Diu. mm.) Staph. aureus Treatment "/1 Solids (o.w.f.)

1% Triphenylbismuthine plus 5% Thermosctting Resin A plus 12% Magnesium Chloride (on resin solids) EXAMPLES ILLUSTRATING GERMICIDAL EFFECTIVENESS OF OTHER ORGANO-BISMUTH COMPOUNDS EXAMPLE 8 Phenylbis(phenylthio)bismuthine ecn The above compound was applied to X 80 cotton fabric at 1% solids (o.w.f.) from dimethylformamide by padding. The fabric was dried for 2 minutes at 225F. The so-finished fabric demonstrated a good initial zone to Staph. aureus of 19.8 mm.

EXAMPLE 9 Tris(p-chlorophenyl)bismuthine TABLE V1 Zones of inhibition No. of (Dia. mm.) Washes Staph. aureus initial 18.3

5 LW 13.0; 14.2p

5 LWC P-C; 12.7p

(21) Initial 15.0

(a) 5l.W P 12.1p

(a) 5 LWC P (:1) Subsequently finished Wl1l1RC1n"/\" The results show the application of the germicidal finish alone did impart a good initial zone of inhibition to Staph. aureus. The subsequent finishing or topping with thermosetting resin A did not improve the activity.

EXAMPLE l Swatches of80 X 80 cotton percale were treated with 1% solids (o.w.f.) of three germicides, tris(alpha, alpha,alpha-trifluoro-m-tolyl)bismuthine (A), diphenylptolylbismuth dichloride (B) and tris(alpha,alpha,alphatrifluoro-m-tolyl)bismuth dichloride (C), from dimethylformamide solutions by conventional padding procedures. The treated swatches were dried and tested for antibacterial activity (agar diffusion method). Results are shown in Table VII.

TABLE VII Zones of Inhibition (mm.)

Various concentrations of triphenylbismuth compounds were evaluated in combination with an alkyl aryl sulfonate on 80 X 80 cotton percale. The method used is described in Applied Microbiology, 10, 74 (1962).

Test solutions of each of the triphenylbismuth compounds in acetone or dimethylformamide were prepared at the following concentrations: 0.20 mg/ml, 0.10 mg/ml.; 0.05 mg/ml. and 0.025 mg/ml. To 8-02. jars there were added 20 ml. portions of a 0.25% aqueous solution of an anionic detergent and some glass beads. The jars were placed in -a water bath at 60C. To each jar there was added 1 ml. of the appropriate test solution and 20 cotton percale (80 X 80) discs of 1 inch diameter. The jars were then shaken in the water bath at 60C. for 10 minutes. The detergent solutions were then decanted from the cloth discs and the discs were rinsed with fresh water for 1 minute. The discs were dried at 50C. for 30 minutes. The cotton discs treated at four levels for each triphenylbismuth compound, namely 0.4% 0.2%, 0.1% and 0.05% on the weight of the detergent, were tested for bactericidal activity by the Colony Count Test.

The results are shown in Table VIII.

TABLE VIl1Continued Performance Rating* Triphcnylbismuth Compound VA MA 1 Didodecanoatc 0.4 0.2

Germicidc concentration, per cent on weight 111' detergent required for indicated activity ratings.

EXAMPLE 12 Various concentrations of bismuthines were evaluated in combination with a commercial anionic detergent on X 80 cotton percale. The method described in Example 11 was used.

The results are shown in Table IX.

TABLE IX Performance Rating Bismuthine VA MA I Tri-p-tol vlbismuthine 0.2 0.1

1-Naphthyldiphenylbismurhine 0.1 0.05

EXAMPLE l3 Various phenoxy and phenylthio triphenylbismuth compounds were evaluated on 80 X 80 cotton percale. The compounds were applied to the fabric from dimethylformamide at 0.05% o.w.f. by conventional padding procedures. The treated swatches were dried at 290F. for 2 minutes. The fabrics were then tested for bactericidal activity by the Colony Count Test described above in Example 24.

The results are shown in Table X.

EXAMPLE 14 Various triphenylbismuth compounds were evaluated on 80 X 80 cotton percale by the procedure of Example 13.

The results are shown in Table XI.

TABLE Xi Triphenylbismuth Compound Performance Rating Formate very active Trifluoroaeetate do.

Stearate do.

EXAMPLE 15 Applications of three different bismuth compounds were made to 80 X 80 cotton percale swatches each at 1% solids (o.w.f.) from dimethylformamide solutions by padding. After application the treated cloths were dried for 2 minutes at 225F. Initial agar diffusion test results are shown in Table XII.

TABLE XII Zones of Inhibition Treatment (Dia. mm.) 7', Solids (o.w.f.) Staph, aureus 1.0% Chlorodiphenylhismuthine 28.8 1.0% Tris-tp-bromuphenyl)bismuthinc P-C; 14.3p

1.0% Tri-p-tolylbismuthinc COMPARATIVE EXXAMPLES DEMONSTRATING THE INEFFECTIVENESS OF OTHER BISMUTH CONTAINING COMPOUNDS EXAMPLE 16 1% Solids (0.w.f.) of bismuth perchlorate was applied to 80 X 80 cotton from diinethylformamide dilution by padding. The treated fabric was dried for 2 minutes at 225F. Agar diffusion tests were made with results as follows:

Aver. Zones of Inhibition (Dia. mm.) 7: o.w.f. Compound Washes Staphaureus 1.0 Bismuth none N Perchlorate EXAMPLE 17 Dispersions of bismuth salts of organic acids found to ing with soap or soap plus chlorine. Results are shown in Table VIII.

TABLE XIII (a) Subsequently finished with Resin The above results demonstrate that the bismuth salts simply are not suited for use in accordance with this in- I vention, in view of the fact that no significant initialbe insoluble in any solvent were prepared as aqueous dispersions using the following formulas:

Parts by Weight Materials A B Bismuth Subacetate 60.0 Bismuth Subgallate 60.0 Bismuth Subsalicylate 60.0 Tamol N (21) 3.0 3.0 3.0 Bentonite (b) 4.5 4.5 4.5 Water (Room Temp.) 232. 232.5 232.5

Total 300.0 300.0 300.0

(a) Dispersing Agent Naphthalene sulfonic acid formaldehyde condensation product. (Sodium salt) (b) Thickener Clay These dispersions were prepared as follows: 60 parts of the bismuth compound was charged into a one quart mill-jar which was half filled with A inch pebbles. To this was added 3 parts of Tamol N followed by 4.5 parts of Bentonite and the water. The jar was closed and placed on a roller mill and run for 24 hours, after which time the aqueous dispersion was separated and bottled. The dispersions were quite stable.

Applications of 1% solids (0.w.f.) of each prepared dispersion were made on 80 X 80 cotton from aqueous dilutions by the padding method. The samples were all dried for 2 minutes at 225F. A portion of each treated sample was aftertreated with 5% solids (0.w.f.) ofResin A plus 12% magnesium chloride (based on the resin solids) followed by drying for 2 minutes at 225F. and then curing for 1.5 minutes at 350F. Agar diffusion tests were performed initially and after a series of washgermicidal activity results from their use, and if initial activity is recorded it is not durable.

APPLICATION OF ORGANO BISMUTI'I COMPOUNDS WITH SURFACE ACTIVE AGENTS As has been pointed out earlientheorganobismuth compounds of this invention are employable with the surface active agents and particularly beneficial resuts are achieved when employed with materials which may be designated as cationic softeners. As will be seen from the examples hereinafter, employing the organo bismuth compounds of this invention with cationic softeners results in good germicidalftnishes, even when relatively small amounts of the organo-bismuth compound are employed in the treating bath. This is particularly evident when theorgano-bismuth compound is exhausted onto the substrate, as for example cellulosic textile material.

EXAMPLE 18 Six individual baths, each containing 100 parts of a detergent solution containing 0.25% of an anionic detergent (dodecyl benzene sulfonate) were entered into Mason type jars. To each of these was added 25, 5, 2.5, 0.5, 0.25 or 0.05 mg. of triphenylbismuthine. A S-gram swatch of X 80 cotton percale was entered into each jar and washed by the Launder-Ometer method for 1, 5 or 10 cycles, as previously described. The amounts of triphenylbismuthine in the baths were estimated to deposit 0.5, 0.1, 0.05, 0.01, 0.005 or 0.001% based on the fabric weight. (It is assumed that all of the triphenylbismuthine goes onto the fabric). After washing and drying the swatches were tested for germicidal activity.

Results in Table XIV show excellent zones of inhibition to Staph. aureus were obtained at 0.5% and good zones at 0.01%. Partial zones wereobtained by buildup at levels as low as 0.005%.

(a) Launder-Ometer washes.

(a) Launder-Ometer washes.

It should be noted that the application of triphenylbismuthine at the 0.5% and at the 0.1% level from detergent baths as in Example 18 to spun nylon gave excellent zones of inhibition against Staph. aureus. These were 23.1; 35.2p at the 0.5% level and 28.3; 30.0p at the 0.1% level.

EXAMPLE 19 Solvent solutions of triphenylbismuthine alone or with commercially known cationic quaternary ammonium compound (Atlas (3-3634) were prepared. Th solvent employed was toluene. I

These solutions, containing varying amounts of tri' phenylbismuthine, were applied to 80 X 80cotton percale by padding at a 90% wet pick-up. The padded samples were then air dried.

Agar diffusion tests were performed as described above.

The results obtained are set f rth in Table XV below.

TABLE XV 7r on Fabric Zones of Inhibition (mm) Cationic Triphenylbismuthine Com- E. coli Staph. aureus pound A B A B 0.06 1.0 S 12.9 P-C 18.2 0.03 1.0 S 12.9 P-C 17.7

A without quaternary with quaternary Table XV demonstrates that greater zones of inhibition are obtained when the triphenylbismuthine is applied at these low concentrations in combination with a cationic quaternary ammonium compound.

EXAMPLE 20 An emulsion was prepared in which triphenylbismuthine was dissolved in toluene and isopropyl alcohol and added to a commercial cationic agent, i.e.. dilauryl dimethyl ammonium chloride. At the same time. corresponding baths without the cationic agent were prepared by diluting the tiphenylbismuthine in dimethylformamide and water. Dilute applications of these formulated preparations were made to 80 X 80 cotton percale by exhaustion.

In the exhaustion procedure the individual cloth samples were entered in mason type jars at 20:1 liquor to cloth ratio and shaken vigorously for 5 minutes. After rinsing and air drying, agar diffusion tests were obtained with the results shown -in table XVl below.

TABLE XVI TPB Cationic Agent Zones of Inhibition (mm) in Bath in Bath E. coli Staph. aureus 0.04 0.08 N-P 17.2 0.032 0.064 VS 15.7 g 0.024 0.048 VS 13.5 0.016 0.032 N 13.1 0.0008 00016 N P-C 0.04 none N N-P 0.032 none N N S 0.024 none N S 0.016 none N S 0.0008 none N VS 'Triphenylbisrnuthine Table XVI above demonstrates that little activity is obtained when triphenylbismuthine is used alone at the low concentrations reported therein. However, when employed with the cationic agent the organo-bismuth compound appears to exhaust onto the fabric and an effective germicidal finish results.

EXAMPLE 21 Example 20 is followed with the exception that the prepared formulations were padded onto X 80 cotton percale at wet pick-up by conventional padding procedures followed by air drying.

The results appear in Table XVII below.

TABLE XVII TPB 7r Cationic Agent Zones of lnhibition(mm) in Bath in Bath E. coli Staph. aureus 0.024 0.048 N VS 0.04 none N VS 0.032 none N VS 0.024 none N VS 0.016 none N 0.0008 none N 'l'riphenylhismuthine Table XVII above demonstrates that very little activity is obtained employing padding procedures at the low concentrations indicated. Employing the cationic agents did not improve the activity significantly.

EXAMPLE 22 Treating baths containing triphenylbismuthine alone or in combination with a non-ionic or cationic agent were made with isopropyl alcohol. These baths were diluted with water to form dilute dispersion type baths.

Swatches of 80 X 80 cotton percale were entered into mason type jars containing a liquorzcloth ratio of 16:1. The jars containing the respective swatches were shaken for 5 minutes. After removing and rinsing, the swatches were air dried and tested.

The results are shown in Table XVIII below.

TABLE XVIII TPB 7c Additive Zones of Inhibition (mm) in Bath in Bath E. coli Staphaureus 0.003 N P-C TABLE XVIII-Continued (l) nonylphenol plus 9 moles ethylene oxide (non-ionic) (2) dilauryl dimcthyl ammonium chloride (cationic) 'Iriplienylhismuthine Table XVIII hereinabove shows that either the nonionic or the cationic additive is needed with the triphenylbismuthine to obtain germicidal properties against Staph. aureus when the concentration of the triphenylbismuthine in the treating solution is of a low order.

EXAMPLE 23 TABLE XIX Zones of Inhibition (mm) TPBD on Fabric E. coli Staph. aureus 0.001 N VS 0.005 N VS 'l'riphenylbismuth dichloride Table XIX above demonstrates that tiphenylbismuth dichloride is active against Staph. aureus at low concentrations.

EXAMPLE 24 Various concentrations of triphenylbismuthine were evaluated in combination with a commercial non-ionic detergent (ethylene oxide condensation of an organic hydroxy compound) on 80 X 80 cotton percale. The application was made by exhaustion.

The baths were prepared as follows:

To 0.25% solids on weight of the fabric of detergent was added the required amount of triphenylbismuthine based on the detergent weight. The combinations were entered into mason type jars and water added in an amount sufficient to make a 20:l liquor to cloth ratio. 10 grams of untreated fabric was entered into each jar. The jars were tightly capped, placed in a Launder- Ometer and run for 25 minutes at 130F. After 25 minutes the samples were removed from the jars and rinsed three times in water at 80F, then air dried. Samples were also run under the same conditions for 5 and cycles. The fabrics were dried after the fifth and tenth cycle.

In some cases 200 parts per million of chlorine was incorporated into the baths. this was done 30 seconds before the cloth samples were entered.

The thus treated samples were then subjected to a Colony Count Test.

The results are shown in Table XX.

TABLE XX Antimicrobial Activity Test Organism Staphylococcus aureus 209 TPB on Wt. No. of

of Detergent Washes Colony Count Test Results 0.05 l l 0.05 5 l 0.05 10 l 005 plus Cl l l 0.05 do. do. 5 VA 0.05 do. do. 10 VA 0.1 l l 0.! 5 I 0.1 10 MA 0.1 l l 0.1 5 l 0.1 10 MA 0.1 plus Cl; l I 0.l do. do. 5 VA 0.1 do. do. 10 VA 0.25 1 MA 0.25 5 VA 0.25 10 VA 0.25 plus Cl, l MA 0.25 do. do. 5 VA 0.25 do. do. 10 VA 0.5 1 VA 0.5 5 VA 0.5 10 VA 0.5 plus Cl I VA 0.5 do. do. 5 VA 0.5 do. do. 10 VA Triphenylbismuthine EXAMPLE 25 Various concentrations of triphenylbismuthine or triphenylbismuth dichloride were evaluated in combination with a commercially available anionic detergent in which dodecyl benzene sulfonate and tripolyphosphate are the principal components in the manner described in Example 24.

The results of the Colony Count Tests are set forth in Table XXI below.

TABLE XXI Antimicrobial activity Test Organism Staphylococcus aureus 209 Triphenyl Triphenyl Bismuth Bismuthine Dichloride I wash 0.05% on weight detergent 1 MA 0.10% do. 1 VA 0.25% do. I VA 050% do. VA VA I wash 200 p.p.m. available Cl,

005% on weight detergent l MA 0.10% do. I VA 025% do. VA VA 050% do. VA VA 5 washes 0.05% on weight detergent I VA 0.25% do. VA VA 050% do. VA VA 5 washes 200 p.p.m. available Cl,

0.05% on weight detergent VA VA 0.10% do. VA VA 0.25% do. VA VA 050% do. VA VA EXAMPLES DEMONSTRATING THE EFFECTIVENESS OF THE ORGANO-BISMUTH COMPOUNDS IN VARIOUS SUBSTRATES EXAMPLE 26 A 20% solids solution was prepared wherein solids of either triphenylbismuthine or triphenylbismuth dichloride were employed with a 10% solids of a commercial cationic quaternary ammonium softening agent (Atlas 63634). The solvent employed was tolu ene. Dilute emulsion of various concentrations were further made by the addition of water. These emulsion type baths were applied to 80 X 80 cotton percale by padding at approximately 80% wet pick-up followed by air drying at room temperature.

Fungicidal tests were performed on each of the various treated fabrics by Modified Mil. Test-F-8261-A (USAF) test method.

The results of this test are shown in Table XXII below.

AN Aspergillus niger CG Chaetomium globosum Triphenylbismuthine Triphenylbismuth dichloride Table XXII above demonstrates that by employing a cationic softener with the germicides of this invention, to finish having increased resistance to mildew (Aspargillus niger) and increased resistance to cellulolytic microorganisms (Chaetomium globosum) is obtained. This latter organism is one which digests cellulose, and produces rotting as distinguished from mere staining, as in the case of mildew.

EXAMPLE 27 0.07% of triphenylbismuthine was applied to the indicated substrate by being sprayed thereon employing a suitable aerosol spraying device. The results of these applications are recorded in Table XXIII.

TABLE XXIII Zones of Inhibition Dia. mm.

Discs. 25.5 mm. Staph. aureus urea-formaldehyde plastic P; 31.0p control none melamine-formaldehyde plastic P-C', 31.2p control none Sitka spruce wood 31.0; 330p control N-S Copper 26.0; 28.0p Control N VS glass P-C; 21 v3p control none The results in Table XXIII demonstrate that the organo-bismuth compounds of the instant invention are effective germicidal agents on a wide variety of substrates which are normally subjected to the development and growth of microorganisms.

EXAMPLE 28 Two sample films thus prepared containing 0.1 or 0.5%

of the triphenylbismuth dichloride additive were then tested by the agar diffusion test method against E. Coli and Staph. aureus.

The results are shown in Table XXIV below.

TABLE XXIV Zones of Inhibition (Dia. mm) T.PB.D.* In Film E. coli Staph. aureus none N N-VS 0.5 P-C; 12.0p 20.1; 23.0p 0.1 N-P 12.2; 16.5p

Triphenylbismuth dichloride Table XXIV demonstrates that by incorporating triphenylbismuth dichloride into the polyethylene antibacterial activity is obtained.

COMPARATIVE EXAMPLES DEMONSTRATING SUPERIORITY OR ORGANO-BISMUTH COMPOUND TO CARBANILIDES EXAMPLE 29 Aqueous detergent solutions containing equal sprayed were sprayed on 80 X 80 cotton from a distance of eight inches for time intervals of from 1 to seconds. Initial activities are reported below.

onds time, cotton cloth to be laundered was added to TABLE XXVI the three solutions.

The results of the test are compared with the results A I achieved with laundering mediums which were identigccondx 55215: cal to those described above. but to which no hypo- 5 p ay d Treatment S. aureus chlorite solution was added. The results are shown in i 1 C --1 P. )(l X Table XXV below. 2 dfl. UCH 1:3; 3 o.

TABLE xxv 4 filo. 22; i233 5 do. 14.7; 160p V 1O 1 Commercial Product (Y) 21.0; 30.7p Zones of lnhibltion 2 do, 31 5p (1311mm) 3 do. 25.4; 35.5p Staph. aureus 4 do, 24 0; 32.7p Purifying Agent No Chlorine Chlorine 5 d 240; 32 l Triphenylbismuthine 18.7; 20.0p 1 "l'riphenylbismuthine 12.9; 14.7p 13.1 2 do. 18.7; 200p 2. Triclilorocarbanilide VS N 3 do. 19.1; 203p 3 3.5tlichloro-3-tri 12.4; 138p N 4 do. 202; 21.5p fluoromethylcarbanilide 5 do. 190; 20.4p

I (X) A 0.190: solids mixture of lributyl tin oxide and quaternary ammonium com ounds.

Table above demonstrates that In the Sec (Y)? mixture of di and tribromosalicylanilides of unknown concentration. onds prior to the introduction of the cotton cloth to the laundering medium purifying agents 2 and 3 were inac- TABLE XXV tivated by the chlorine, while the bismuthine com pound of this invention was not. Thus the compounds Mara e Zone of this invention may be applied from and employed in Diame ter (mm.) detergent formulations containing or to be employed wash aureus with chlorinebleaching agents without disadvantage. Triphenylbismmhine mm 1%; 204p COMPARATIVE EXAMPLE DEMONSTRATING iiiiii i ii'ifi ADVANTAGE OF TRlPHENYLBlSMUTHlNE ka 12-; fi er OVER NEOMYVCIN SULFATE A COMMERCIAL Commercial Product X lnitial 14:7 16:08

GERMICIDE 5 LW N 5 LWC vs EXAMPLE 30 15 LW N 15 LWC N For comparison purposes triphenylbismuthine or ne- Commercial Prod ct Y 7 Initial 24.0; p I omycin sulfate (a commercially available purifying fing S ish) was applied to 80X 80 cotton percale at 1.0% and 15 Lvv N 0.5% solids (0.w.f.) by the padding procedures. The apl5 Lwc N plications of triphenylbismuthine were made from dif i i dyllunonsdwhfereas the neomyclmfsul- Table XXVIl above demonstrates that. as compared a app 1on5 were ma 6 aquepus so u 9 40 with commerically available germicidal finishes that of After padding, the treated fabrics were dried for 2 minc the present invention 18 markedly superior. A series of utes at 225 F. and sub ected to 5, 10, 15 or 20 LW or LWC h th d d d t t d b th similar comparisons carried out employing concentrais 3 g p y e a 1 tions of triphenylbismuthine as low as 0.05% produced Slon me O or l ac ac m substantially identical results.

The results of this comparison showed neomycin sulfate treatments had little or no activity against Staph. THE INTERRELATION BETWEEN aureus after chlorine washing, whereas the triphenyl- TRIPHENYLBISMUTHINE AND bismuthine treatments retained activity through 10 TRIPHENYLBISMUTH DICHLORIDE AND chlorine washes. TRlPHENYLBISMUTl-l HYDROXYCHLORIDE COMPARATIVE EXAMPLES DEMONSTRATING Because it has almost invariably been noted that fab- SUPERIORITY 0F TRIPHENYLBISMUTHINE rics treated with organo-bismuth compounds in accor- OVER OTHER OMM C L ICI dance with this invention display larger zones of inhibition in durability testing when they are laundered ern- EXAMPLE 31 ploying a hypochlorite bleach in the wash liquor (when In order to demonstrate the superiority of the orzones are compared at same number of washes in gano-bismuth compounds of this invention as a germiwhich hypochlorite is not employed) it was decided to cidal finish for textile materials, paper and the like, a investigate the possibility of a chemical reaction beformulation capable of being sprayed as by aerosol tween the bismuth and the hypochlorite. techniques was prepared, containing 0.275% of triphenylbismuthine based on the weight of the solvent EXAMPLE 32 p and propellant. The solvent was carbon tetrachloride A. 250 milliliters of a hypochlorite solution containand the propellantwasaFreon propellant. This compoing 5.57 i .12% of chlorine were reacted with 4.4 sition and two other commercially available germicidal grams l0 milliequivalents) or triphenylbismuthine. Tifinishes available in containers from which they can be tration of the slurry after 4 hours of stirring at room temperature showed a loss of 0.75 milliequivalents of hypochlorite per milliequivalent of triphenylbismuthine.

Analysis of the resulting orange solid was as follows:

Analysis: C H Cl Found: 46.00 3.2l 3.97 6.5l 6.59 Calculated: 441 3.04 3.26 7.22

The calculation was for triphenylbismuth hydroxychloride. 1

B. The reaction set forth in (A) above was repeated, only 2 equivalents of hypochlorite per equivalent of triphenylbismuthine were employed. Titration showed a loss of 1.7 equivalents of hypochlorite after 16 hours. Analysis, however, indicated that the same product as was obtained in (A) was obtained here, i.e., triphenylbismuth hydroxychloride, although the titration showed twice as much hypochlorite was used.

Analysisl C H 0 Found.

The resulting product, as in (A), was an orange solid and, as in the case of the product of (A), decomposes vigorously at 105C.

The results of Examples 32 (A) and (B) demonstrate that a reaction product is formed from the reaction between triphenylbismuthine and sodium hypochlorite.

EXAMPLE 33 TABLE XXVIII 7c Solids Aver, Zone (Dia. mm) Applied (owf) Washes E. coli S. aureus 0.5 none 14.3 23.6 0.5 LW N S-C', -l2.3p 0.5 l0 LW N N 0.5 5 LWC S l6.9 0.5 l0 LWC N l5.2; l6.8p 0.25 none P 15.7; 20.0p 0.25 5 LW N VS 0.25 10 LW N N 0.25 5 LWC N l6.0 0.25 l0 LWC N l2.0; 13.7p

The results set forth in Table XXVIII demonstrate limited durability of germicidal activity on the finished cotton when the laundering procedure does not involve the use of sodium hypochlorite or chlorine in the wash liquor. These results in general terms correspond to those produced by the application of organo-bismuth compounds of the instant invention, as has been demonstrated hereinabove.

Thus it is that triphenylbismuthine reacts with chlorine or sodium hypochlorite under conditions normally experienced in laundering operations to produce triphenylbismuth hydroxychloride which is itself an effective germicide. This is a unique advantage for the use of one of the preferred compounds of this invention, i.e., triphenylbismuthine, and distinguishes it from such commercial germicides as ncomycin sulfate and various carbanilides, which are deactivated by chlorine.

One of the principal advantages of a second preferred species, i.e., triphenylbismuth dichloride is its stability and effectiveness over a wide range of pH. This is important, particularly in commerical laundering operations where the pH, during the wash cycle, may be above 8.5, but in subsequent rinse cycles the pH of the rinse may actually be rendered acidic. By using a germicide that remains effective over a wide pH range, it will be apparent that the germicide may be incorporated into the laundry cycle at any stage.

In this regard, it has been determined that triphenylbismuth dichloride is stable at a pH of 7.5 or below, but

that at a pH of 8.5 or higher the dichloride is hydrolyzed to triphenylbismuth hydroxychloride and to some extent to triphenylbismuthine. It has further been determined that the dichloride does not regenerate under acid conditions.

Biologically, triphenylbismuthine and triphenylbismuth hydroxychloride have the same general level of activity, while the dichloride itself demonstrates greater activity yet as is noted above, under alkaline conditions, i.e., pH 8.5 or higher, the active components are actually the hydroxychloride and triphenyl' bismuthine.

Thus, triphenylbismuthine, triphenylbismuth dichloride, triphenylbismuth hydroxychloride are all closely related and the use of one of these compounds under certain conditions in laundering operations may well result in the presence of one or more of the remaining compounds frequently with an enhanced or synergistic result.

As has been pointed out hereinabove, the organobismuth compounds contemplated for use in accordance with this invention are not deactivated by chlorine whether it be present through the addition of sodium hypochlorite to a laundering medium or whether it is generated in situ in such medium as from such materials as sodium dichlorotriazinetrione or potassium dichloroisocyanurate. Further, the organobismuth compounds of this invention may be readily formulated into such solid bleach composition including those containing sodium perborate and sodium persulfate. I

A further advantage of the preferred organobismuth compounds of this invention is their relative low toxicity when compared with a number of known germicides as determined by a standard test conducted on rats. This is evident from Table XXIX.

TABLE XXIX Rat L,,50 oral. mg/kg.

Hexachlorophene -200 Phenylmercury Propionate I00 Phenylmercury Acetate 27 Zinc l-Hydroxy-2pyridinethione 207 Triphenylbismuthine 4,580 Triphenylbismuth Dichloride 770 Triphenylbismuth Hydroxychloride 510 In the above Table the larger the number the less toxic the compound. It will thus be seen that the preferred compounds of this invention may be described as being of low toxicity.

It will be apparent from this and the remaining portions of the description of the instant invention that the use of organo-bismuth compounds as germicidal agents is contemplated for numerous applications not specifically demonstrated hereinabove.

I claim:

1. A method for protecting a medium susceptible to attack by fungi and bacteria which comprises applying to the locus to be protected an effective amount of a bismuth compound selected from the group consisting of R' BiX and RnBiX n, wherein n is 1 to 2, X is selected from the group consisting of halogen, oxygen, carboxylate, phenoxide and mercaptide and R and R are aryl.

2. The method of claim 1 wherein the bismuth compound is triphenylbismuth dihydroxide.

3. The method of claim 1 wherein the bismuth compound is triphenylbismuth dichloride.

4. The method of claim 1 wherein the bismuth compound is triphenylbismuth diacetate.

5. The method of claim 1 wherein the bismuth compound is diphenylbismuth chloride.

6. The method of claim 1 wherein the bismuth compound is phenylbismuth dichloride.

7. A fungi and bacteria resistant plastic material comprising a plastic composition and an effective amount of a bismuth compound selected from the group consisting of R SBlXZ and RnBiX n, wherein n is l to 2, X is selected from the group consisting of halogen, oxygen, carboxylate, phenoxide and mercaptide and R and R are aryl.

8. A fungi and bacteria resistant paper comprising the paper and an effective amount of a bismuth compound selected from the group consisting of R' BiX and RnBiX -n, wherein n is l to 2, X is selected from the group consisting of halogen, oxygen, carboxylate, phenoxide and mercaptide, and R and R are aryl.

9. A fungi and bacteria resistant cloth comprising the cloth and an effective amount of bismuth compound selected from the group consisting of R BiX and RnBiX n, wherein n is 1 to 2, X is selected from the group consisting of halogen, oxygen, carboxylate,

phenoxide and mercaptide, and R and R are aryl. 

2. The method of claim 1 wherein the bismuth compound is triphenylbismuth dihydroxide.
 3. The method of claim 1 wherein the bismuth compound is triphenylbismuth dichloride.
 4. The method of claim 1 wherein the bismuth compound is triphenylbismuth diacetate.
 5. The method of claim 1 wherein the bismuth compound is diphenylbismuth chloride.
 6. The method of claim 1 wherein the bismuth compound is phenylbismuth dichloride.
 7. A fungi and bacteria resistant plastic material comprising a plastic composition and an effective amount of a bismuth compound selected from the group consisting of R''3BiX2 and RnBiX3 n, wherein n is 1 to 2, X is selected from the group consisting of halogen, oxygen, carboxylate, phenoxide and mercaptide and R'' and R are aryl.
 8. A fungi and bacteria resistant paper comprising the paper and an effective amount of a bismuth compound selected from the group consisting of R''3BiX2 and RnBiX2 n, wherein n is 1 to 2, X is selected from the group consisting of halogen, oxygen, carboxylate, phenoxide and mercaptide, and R'' and R are aryl.
 9. A fungi and bacteria resistant cloth comprising the cloth and an effective amount of bismuth compound selected from the group consisting of R''3BiX2 and RnBiX3 n, wherein n is 1 to 2, X is selected from the group consisting of halogen, oxygen, carboxylate, phenoxide and mercaptide, and R'' and R are aryl. 